DE19649062A1 - Liquid, oil-miscible carotenoid preparations - Google Patents
Liquid, oil-miscible carotenoid preparationsInfo
- Publication number
- DE19649062A1 DE19649062A1 DE19649062A DE19649062A DE19649062A1 DE 19649062 A1 DE19649062 A1 DE 19649062A1 DE 19649062 A DE19649062 A DE 19649062A DE 19649062 A DE19649062 A DE 19649062A DE 19649062 A1 DE19649062 A1 DE 19649062A1
- Authority
- DE
- Germany
- Prior art keywords
- oil
- liquid
- carotenoid
- miscible
- preparations according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/179—Colouring agents, e.g. pigmenting or dyeing agents
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/40—Colouring or decolouring of foods
- A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
- A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
- A23L5/44—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/67—Vitamins
- A61K8/671—Vitamin A; Derivatives thereof, e.g. ester of vitamin A acid, ester of retinol, retinol, retinal
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
- A61K9/1075—Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/904—Specified use of nanostructure for medical, immunological, body treatment, or diagnosis
- Y10S977/926—Topical chemical, e.g. cosmetic or sunscreen
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epidemiology (AREA)
- Food Science & Technology (AREA)
- Birds (AREA)
- Engineering & Computer Science (AREA)
- Pharmacology & Pharmacy (AREA)
- Nutrition Science (AREA)
- Biophysics (AREA)
- Dermatology (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Medicinal Chemistry (AREA)
- Cosmetics (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Medicinal Preparation (AREA)
- Fodder In General (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Colloid Chemistry (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
Die Erfindung betrifft flüssige, mit Öl mischbare Carotinoid-Zu bereitungen, Verfahren zu deren Herstellung sowie ihre Verwendung als Zusatz zu Tierfuttermitteln, Lebensmitteln, Kosmetika und Pharmazeutika.The invention relates to liquid, oil-miscible carotenoid additives preparations, processes for their production and their use as an additive to animal feed, food, cosmetics and Pharmaceuticals.
Carotinoide bilden eine Gruppe von Farbpigmenten mit gelber bis roter Farbtonnuance, die in der Natur weitverbreitet vorkommen und vielen Nahrungsmitteln eine charakteristische Färbung ver leihen. Als wichtigste Vertreter dieser Stoffklasse seien β-Caro tin, Astaxanthin, β-Apo-8'-carotinal, Canthaxanthin, Lycopin und Citranaxanthin genannt. Sowohl für die Lebensmittel- und Futter mittelindustrie als auch für die pharmazeutische Technologie stellen diese synthetisch herstellbaren Substanzen z. B. als Er satz für künstliche Farbstoffe wichtige Farbkörper dar und sind zum Teil wegen ihrer Pro-Vitamin-A-Aktivität von Interesse.Carotenoids form a group of color pigments with yellow to red hues that are widespread in nature and many foods have a characteristic color lend. The most important representatives of this class of substances are β-caro tin, astaxanthin, β-apo-8'-carotinal, canthaxanthin, lycopene and Called citranaxanthin. Both for food and feed medium industry as well as for pharmaceutical technology make these synthetically producible substances such. B. as He are important color bodies for artificial dyes partly of interest because of its pro-vitamin A activity.
Alle Carotinoide sind in Wasser unlöslich, während in Fetten und Ölen eine jedoch nur geringe Löslichkeit gefunden wird. Diese be grenzte Löslichkeit sowie die hohe Oxidationsempfindlichkeit stehen einer direkten Anwendung der relativ grobkörnigen bei der Synthese erhaltenen Produkte in der Einfärbung von Lebens- und Futtermitteln entgegen, da die Substanzen in grobkristalliner Form nur schlecht resorbiert werden und somit nur schlechte Färbungsergebnisse liefern.All carotenoids are insoluble in water, while in fats and Oil is found to have a low solubility. These be limited solubility and high sensitivity to oxidation are a direct application of the relatively coarse grain in the Products obtained in the coloring of food and synthesis Feed, as the substances are in coarse crystalline form Form are poorly absorbed and therefore only poor Deliver coloring results.
Nur durch gezielt hergestellte Formulierungen, in denen die Wirk stoffe in fein verteilter Form und gegebenenfalls durch Schutz kolloide oxidationsgeschützt vorliegen, lassen sich bei der di rekten Einfärbung von Lebensmitteln verbesserte Farbausbeuten er zielen. Außerdem führen diese in Futtermitteln verwendeten Formu lierungen zu einer höheren Bioverfügbarkeit der Carotinoide und damit indirekt zu besseren Färbungseffekten z. B. bei der Ei dotter- oder Fischpigmentierung.Only through specifically produced formulations in which the effectiveness fabrics in finely divided form and, if necessary, through protection colloids are protected against oxidation, can be in the di correct coloring of food he improved color yields aim. In addition, these formu used in animal feed higher bioavailability of carotenoids and thus indirectly to better coloring effects z. B. in the egg yolk or fish pigmentation.
In der Futtermittelindustrie, speziell im Bereich Fishfarming werden aus der Gruppe der Carotinoide besonders Astaxanthin und Canthaxanthin zum Färben von u. a. Lachsen, Forellen und Shrimps verwendet. Dabei werden die Wirkstoffe in Form von Trockenpulvern eingesetzt, in denen das dispergierte Carotinoid durch z. B. Gelatine und Zucker als Schutzkolloide vor oxidativem Abbau ge schützt wird. Das Trockenpulver wird dabei während der Futter mittelherstellung direkt im Extrusions- bzw. Pelletierverfahren mit verarbeitet, wobei die unter den Herstellbedingungen auftre tenden Streßfaktoren wie Hitze, Feuchtigkeit und Lufteinfluß häufig zu unerwünschten Produktschädigungen und damit zu Wirk stoffverlusten führen.In the feed industry, especially in the area of fish farming from the group of carotenoids especially astaxanthin and Canthaxanthin for dyeing u. a. Salmon, trout and shrimp used. The active ingredients are in the form of dry powders used in which the dispersed carotenoid by z. B. Gelatin and sugar as protective colloids against oxidative degradation protects. The dry powder is used during the feed Medium production directly in the extrusion or pelletizing process processed with, which occurs under the manufacturing conditions tendency stress factors such as heat, humidity and air influence often to undesirable product damage and thus to effect lead to material losses.
Zur Verringerung dieser Wirkstoffverluste kann, wie in WO 96/23420 beschrieben, feingemahlenes Astaxanthin in Öl suspen diert werden, um anschließend auf das bereits extrudierte bzw. pelletierte Futtermittel aufgesprüht zu werden. Sowohl die Bio verfügbarkeit und damit auch die erzielte Farbwirkung als auch die chemische Stabilität der Wirkstoffe sind hierbei nicht zu friedenstellend.To reduce this loss of active ingredient, as in WO 96/23420, finely ground astaxanthin in oil be dated in order to then on the already extruded or pelleted feed to be sprayed on. Both the bio availability and thus the color effect achieved as well the chemical stability of the active ingredients are not too peaceful.
In anderen Verfahren, beschrieben in WO 94/19411, wird kristalli nes β-Carotin in Gegenwart einer wäßrigen Schutzkolloid-Lösung gemahlen und anschließend durch kurzzeitiges Erhitzen bis zum Schmelzpunkt in eine amorphe Modifikation überführt.In other processes, described in WO 94/19411, crystallization takes place nes β-carotene in the presence of an aqueous protective colloid solution ground and then by briefly heating to Melting point converted into an amorphous modification.
Auch diese Formulierung, sowie die zahlreich beschriebenen, wäßrigen Carotinoid-Dispersionen und O/W-Emulsionen, in denen der Wirkstoff in Gegenwart stabilisierender Schutzkolloide vorliegt, sind ebenfalls ungeeignet, da sie mit Ölen nicht mischbar sind.This wording, as well as the many described, aqueous carotenoid dispersions and O / W emulsions in which the Active ingredient is present in the presence of stabilizing protective colloids, are also unsuitable because they are not miscible with oils.
GB 993 138 beschreibt ein Verfahren zur Herstellung von u. a. Vitamin A-haltigen Beadlets, das dadurch gekennzeichnet ist, daß man Vitamin A in eine wäßrige, Gelatine-haltige Schutzkolloid- Lösung dispergiert und diese Dispersion durch zusätzliches Suspendieren in Öl in Form von Beadlets ausfällt. Aufgrund von zu großen Partikeldurchmessern von über 300 µm und der damit verbun denen physikalischen Instabilität solcher Suspensionen bzw. Emul sionen, sind solche Systeme für die oben genannte Anwendung von flüssigen Carotinoiden-Zubereitungen ungeeignet.GB 993 138 describes a process for the preparation of u. a. Beadlets containing vitamin A, which is characterized in that to convert vitamin A into an aqueous protective colloid containing gelatin Dispersed solution and this dispersion by additional Suspending in oil in the form of beadlets fails. Because of too large particle diameters of over 300 µm and the associated those physical instability of such suspensions or emulsions sions, are such systems for the above application of liquid carotenoid preparations unsuitable.
Es bestand daher die Aufgabe, Carotinoid-Formulierungen zu ent wickeln, die die oben genannten Nachteile nicht aufweisen.It was therefore the task of ent to carotenoid formulations wrap that do not have the disadvantages mentioned above.
Diese Aufgabe wurde erfindungsgemäß mit der Bereitstellung flüssiger, mit Öl mischbarer Carotinoid-Zubereitungen gelöst, die dadurch gekennzeichnet sind, daß sie als doppelte Dispersions systeme eine wäßrig-disperse Phase mit einem Partikeldurchmesser kleiner 100 µm, in der schutzkolloid-stabilisierte Teilchen eines oder mehrerer Carotinoide dispergiert vorliegen, in einem Öl als Dispersionsmittel enthalten.This object was achieved with the provision liquid, oil-miscible carotenoid preparations, which are characterized in that they are double dispersions systems an aqueous disperse phase with a particle diameter smaller than 100 µm, in the protective colloid-stabilized particles or more carotenoids are dispersed in an oil as Contain dispersants.
Die Erfindung betrifft außerdem ein Verfahren zur Herstellung von flüssigen, mit Öl mischbaren Carotinoid-Zubereitungen dadurch ge kennzeichnet, daß man eine wäßrige, schutzkolloidhaltige Disper sion eines oder mehrerer Carotinoide in Gegenwart eines Emul gators in Öl emulgiert.The invention also relates to a method for producing thereby liquid, oil-miscible carotenoid preparations indicates that an aqueous, protective colloidal Disper sion of one or more carotenoids in the presence of an emul emulsified in oil.
Durch die erfindungsgemäße Kombination wäßriger Dispergierverfah ren von fettlöslichen Wirkstoffen mit einem weiteren Wasser-in- Öl-Emulgierschritt lassen sich Produkte mit neuen überraschenden Eigenschaftsprofilen erhalten.The combination of aqueous dispersing process according to the invention fat-soluble active ingredients with another water-based Oil emulsification step can be products with new surprising Get property profiles.
Die so erhältlichen flüssigen Carotinoid-Zubereitungen lassen sich hervorragend als Farbstoffe bzw. Zusätze für Lebens- und/oder Futtermittel sowie für kosmetische oder pharmazeutische Dar reichungsformen verwenden.Leave the liquid carotenoid preparations available in this way are excellent as dyes or additives for food and / or Feed as well as for cosmetic or pharmaceutical dar use dosage forms.
Die Herstellung der wäßrig-dispersen Phase, die schutzkolloid- stabilisierte Teilchen eines oder mehrerer Carotinoide enthält, ist bereits Gegenstand zahlreicher Publikationen und Patent schriften, wie beispielsweise EP-B-0 278 284, EP-B-0 065 193, DE-A-37 02 030, DE-A-25 34 091 sowie einer Zusammenfassung in R.A. Morton, Fat Soluble Vitamins, Intern. Encyclopedia of Food and Nutrition, Bd. 9, Pergamon Press 1970, S. 134-139.The production of the aqueous disperse phase, the protective colloid contains stabilized particles of one or more carotenoids, is already the subject of numerous publications and patents publications such as EP-B-0 278 284, EP-B-0 065 193, DE-A-37 02 030, DE-A-25 34 091 and a summary in R.A. Morton, Fat Soluble Vitamins, Intern. Encyclopedia of Food and Nutrition, Vol. 9, Pergamon Press 1970, pp. 134-139.
Aus der Vielzahl der oben zitierten, wäßrigen Dispergierverfahren ist das sogenannte Mikronisierverfahren gemäß EP-B-0 065 193 für die vorliegenden Zwecke besonders geeignet. Dieses Verfahren ist dadurch gekennzeichnet, daß man ein Carotinoid in einem flüchti gen, mit Wasser mischbaren, organischen Lösungsmittel bei Tempe raturen zwischen 50°C und 200°C innerhalb einer Zeit von weniger als 10 Sekunden löst und aus der erhaltenen Lösung sofort durch schnelles Mischen mit einer wäßrigen Schutzkolloid-Lösung das Carotinoid in kolloid-disperser Form ausfällt. Bezüglich der Ein zelheiten wird auf die EP-B-0 065 193 verwiesen.From the multitude of the aqueous dispersion processes cited above is the so-called micronizing process according to EP-B-0 065 193 for the present purposes particularly suitable. This procedure is characterized in that a carotenoid in a volatile organic water-miscible organic solvents at Tempe temperatures between 50 ° C and 200 ° C within a time of less dissolves as 10 seconds and immediately through from the solution obtained rapid mixing with an aqueous protective colloid solution Carotenoid in a colloid-disperse form fails. Regarding the one For details, see EP-B-0 065 193.
Die Carotinoide, die im Rahmen der Erfindung eingesetzt werden können, sind die bekannten, zugänglichen, natürlichen oder synthetischen Vertreter dieser Klasse von Verbindungen, die als farbgebende Mittel brauchbar sind, z. B. β-Carotin, Astaxanthin, Lycopin, Bixin, Zeaxanthin, Cryptoxanthin, Citranaxanthin, Lutein, Canthaxanthin, β-Apo-4'-carotinal, β-Apo-8'-carotinal, β- Apo-12'-carotinal, β-Apo-8'-carotinsäure sowie Ester von hydroxy- und carboxyhaltigen Vertretern dieser Gruppe, z. B. die niederen Alkylester und vorzugsweise die Methyl- und Ethylester. Besonders bevorzugt werden die bisher technisch gut zugänglichen Caroti noide wie β-Carotin, Astaxanthin, Canthaxanthin, Lycopin, β- Apo-8'-carotinal und β-Apo-8'-carotinsäureester einzeln oder als Mischung verwendet. Die Wirkstoffe liegen dabei in öliger, amor pher und/oder kristalliner Form vor, wobei im Hinblick auf eine optimale Bioverfügbarkeit die öligen und amorphen Modifikationen bevorzugt sind.The carotenoids that are used in the context of the invention can be the known, accessible, natural or synthetic representatives of this class of compounds that are considered colorants are useful, e.g. B. β-carotene, astaxanthin, Lycopene, bixin, zeaxanthin, cryptoxanthin, citranaxanthin, Lutein, canthaxanthin, β-apo-4'-carotinal, β-apo-8'-carotinal, β- Apo-12'-carotenal, β-apo-8'-carotenic acid and esters of hydroxy and carboxy-containing representatives of this group, e.g. B. the lower Alkyl esters and preferably the methyl and ethyl esters. Especially preference is given to the previously technically accessible caroti noides such as β-carotene, astaxanthin, canthaxanthin, lycopene, β- Apo-8'-carotenal and β-apo-8'-carotenic acid esters individually or as Mixture used. The active ingredients are in an oily, cupid pher and / or crystalline form, with regard to a optimal bioavailability the oily and amorphous modifications are preferred.
Nach dem o.g. Mikronisierverfahren sind zur Durchführung der er sten Dispergierstufe als Teil des Gesamtverfahrens vor allem wassermischbare, thermisch stabile, flüchtige, nur Kohlenstoff, Wasserstoff und Sauerstoff enthaltene Lösungsmittel wie Alkohole, Ether, Ester, Ketone und Acetale geeignet. Vorzugsweise werden Ethanol, n-Propanol, Isopropanol, 1,2-Butandiol-1-methylether, 1,2-Propandiol-1-n-propylether oder Aceton verwendet. Allgemein verwendet man zweckmäßig solche Lösungsmittel, die mindestens zu 10% wassermischbar sind, einen Siedepunkt unter 200°C aufweisen und/oder weniger als 10 Kohlenstoffe haben.After the above Micronizing processes are used to carry out the Most of all the dispersion stage as part of the overall process water miscible, thermally stable, volatile, only carbon, Solvents containing hydrogen and oxygen, such as alcohols, Suitable ethers, esters, ketones and acetals. Preferably be Ethanol, n-propanol, isopropanol, 1,2-butanediol-1-methyl ether, 1,2-propanediol-1-n-propyl ether or acetone is used. General one expediently uses such solvents which are at least too 10% are water miscible, have a boiling point below 200 ° C and / or have less than 10 carbons.
Als Schutzkolloide werden beispielsweise Gelatine, Fischgelatine, Stärke, Dextrin, Pflanzenproteine, Pektin, Gummi-Arabikum, Kasein, Kaseinat oder Mischungen davon verwendet. Es können aber auch Polyvinylalkohol, Polyvinylpyrrolidon, Methylcellulose, Carboxymethylcellulose, Hydroxypropylcellulose und Alginate ein gesetzt werden. Bezüglich näherer Einzelheiten wird auf R.A. Morton, Fat Soluble Vitamins, Intern. Encyclopedia of Food and Nutrition, Bd. 9, Pergamon Press 1970, S. 128-131, verwiesen. Zur Erhöhung der mechanischen Stabilität des Endproduktes ist es zweckmäßig, dem Kolloid einen Weichmacher zuzusetzen, wie Zucker oder Zuckeralkohole, z. B. Saccharose, Glucose, Lactose, Invert zucker, Sorbit, Mannit oder Glycerin.Protective colloids are, for example, gelatin, fish gelatin, Starch, dextrin, plant proteins, pectin, gum arabic, Casein, caseinate or mixtures thereof are used. But it can also polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, Carboxymethyl cellulose, hydroxypropyl cellulose and alginates be set. For more details, see R.A. Morton, Fat Soluble Vitamins, Intern. Encyclopedia of Food and Nutrition, Vol. 9, Pergamon Press 1970, pp. 128-131. For It is an increase in the mechanical stability of the end product expedient to add a plasticizer to the colloid, such as sugar or sugar alcohols, e.g. B. sucrose, glucose, lactose, invert sugar, sorbitol, mannitol or glycerin.
Die Mengen an Schutzkolloid, Weichmacher und Carotinoid werden im allgemeinen so gewählt, daß ein Endprodukt erhalten wird, das zwischen 0,01 und 10 Gew.-%, vorzugsweise zwischen 0,5 und 5 Gew.-%, Carotinoid, 2 bis 20 Gew.-% eines Schutzkolloids, 2 bis 20 Gew.-% eines Weichmachers, alle Prozentangaben bezogen auf die Gesamtmasse der fertigen Emulsion, sowie gegebenenfalls geringe Mengen eines Stabilisators enthält.The amounts of protective colloid, plasticizer and carotenoid are in the generally chosen so that a final product is obtained, the between 0.01 and 10% by weight, preferably between 0.5 and 5% by weight, carotenoid, 2 to 20% by weight of a protective colloid, 2 to 20 wt .-% of a plasticizer, all percentages based on the Total mass of the finished emulsion, and possibly a small one Contains amounts of a stabilizer.
Zur Erhöhung der Stabilität des Wirkstoffes gegen oxidativen Ab bau ist es vorteilhaft, Stabilisatoren wie α-Tocopherol, t-Butyl hydroxy-toluol, t-Butylhydroxyanisol, Ascorbinsäure oder Ethoxy quin zuzusetzen. Sie können entweder der wäßrigen oder der Lösungsmittel-Phase zugesetzt werden, vorzugsweise werden sie je doch gemeinsam mit den Farbstoffen und gegebenenfalls zusätz lichen Emulgatoren in der Lösungsmittel-Phase gelöst.To increase the stability of the active ingredient against oxidative Ab It is advantageous to build stabilizers such as α-tocopherol, t-butyl hydroxytoluene, t-butylhydroxyanisole, ascorbic acid or ethoxy add quin. You can use either the watery or the Solvent phase are added, preferably they are each but together with the dyes and possibly additional union emulsifiers dissolved in the solvent phase.
Als Emulgatoren in der primären Dispersion können beispielsweise Ascorbylpalmitat, Polyglycerin-Fettsäureester, Sorbitan-Fett säureester, Propylenglycol-Fettsäureester oder Lecithin in einer Konzentration von 0 bis 200 Gew.-%, vorzugsweise 10 bis 150 Gew.-%, besonders bevorzugt 15 bis 80 Gew.-%, bezogen auf das/die Caroti noid(e), verwendet werden.As emulsifiers in the primary dispersion, for example Ascorbyl palmitate, polyglycerol fatty acid ester, sorbitan fat acid esters, propylene glycol fatty acid esters or lecithin in one Concentration from 0 to 200% by weight, preferably 10 to 150% by weight, particularly preferably 15 to 80% by weight, based on the carotid (s) noid (e) can be used.
Durch Zusatz von in der Lebens- und Futtermittelindustrie zuge lassenen Konservierungsstoffen wie beispielsweise Sorbinsäure, Natrium-Sorbat, Benzoesäure, Natrium-Benzoat oder PHB-Ester wie 4-Hydroxy-methylbenzoat oder 4-Hydroxy-propylbenzoat in einer Konzentration von 0 bis 200 Gew.-%, vorzugsweise 10 bis 150 Gew.-%, besonders bevorzugt 15 bis 80 Gew.-%, bezogen auf das/die Caroti noid(e), kann eine unerwünschte mikrobielle Zersetzung der wäßri gen Dispersion verhindert werden.By adding in the food and feed industry preservatives such as sorbic acid, Sodium sorbate, benzoic acid, sodium benzoate or PHB esters such as 4-hydroxy methyl benzoate or 4-hydroxy propyl benzoate in one Concentration from 0 to 200% by weight, preferably 10 to 150% by weight, particularly preferably 15 to 80% by weight, based on the carotid (s) noid (e), an undesirable microbial decomposition of the aq against dispersion.
Unter Umständen kann es auch vorteilhaft sein, zusätzlich zum Carotinoid oder dem Gemisch mehrerer Carotinoide im ersten Dis pergierschritt ein physiologisch zugelassenes Öl wie beispiels weise Sesamöl, Maiskeimöl, Baumwollsaatöl, Sojabohnenöl oder Erd nußöl sowie Ester mittelkettiger pflanzlicher Fettsäuren in einer Konzentration von 0 bis 500 Gew.-%, vorzugsweise 10 bis 300 Gew.-%, besonders bevorzugt 20 bis 100 Gew.-%, bezogen auf das/die Caroti noid(e), zu lösen, das dann gemeinsam mit den Wirkstoffen und den genannten Zusatzstoffen beim Mischen mit der wäßrigen Phase extrem feinteilig ausgefällt wird.It may also be advantageous in addition to Carotenoid or the mixture of several carotenoids in the first dis step a physiologically approved oil such as Sesame oil, corn oil, cottonseed oil, soybean oil or earth nut oil and esters of medium chain vegetable fatty acids in one Concentration from 0 to 500% by weight, preferably 10 to 300% by weight, particularly preferably 20 to 100% by weight, based on the carotid (s) noid (e) to solve, which then together with the active ingredients and the additives mentioned when mixing with the aqueous phase is precipitated extremely fine.
Je nach Art und Menge des verwendeten Schutzkolloids erhält man als wäßrige Carotinoid-Dispersion eine tiefgefärbte viskose Flüssigkeit, die im Falle eines gelierfähigen Kolloids gelartig erstarrt und in der die mittlere Teilchengröße der Carotinoide weniger als 0,2 µm beträgt.Depending on the type and amount of protective colloid used, one obtains a deeply colored viscous as an aqueous carotenoid dispersion Liquid that is gel-like in the case of a gellable colloid solidifies and in which the average particle size of the carotenoids is less than 0.2 µm.
Die Entfernung des Lösungsmittels kann je nach Siedepunkt in an sich bekannter Weise, z. B. durch Destillation, gegebenenfalls unter vermindertem Druck, oder durch Extraktion mit einem mit Wasser nicht mischbaren Lösungsmittel, erfolgen.The removal of the solvent may vary depending on the boiling point known way, e.g. B. by distillation, if appropriate under reduced pressure, or by extraction with a Water-immiscible solvents.
Anders als im oben erwähnten Stand der Technik, wonach die wäßri gen Wirkstoff-Dispersionen in ein Trockenpulver überführt werden, führt im erfindungsgemäßen Verfahren die zusätzliche Wasser-in- Öl-Emulgierung zu einer neuen Flüssigformulierung in Form einer doppelten Dispersion.Unlike in the above-mentioned prior art, according to which the aq gene active ingredient dispersions are transferred to a dry powder, performs the additional water-in Oil emulsification to a new liquid formulation in the form of a double dispersion.
Dabei wird unter Verwendung eines Emulgators eine Wasser- in-Öl- Emulsion gebildet, in der die Wasserphase schutzkolloidstabili sierte Carotinoid-Nanoteilchen enthält. Als Emulgatoren kommen an sich bekannte W/O-Emulgatoren mit einem HLB-Wert kleiner 10, ins besondere von 2 bis 6 in Betracht (vgl. H.P. Fiedler, Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzende Gebiete, 1996, Seiten 753 ff). Typische Vertreter dieser Emulgatorklasse sind Partialfettsäureester mehrwertiger Alkohole z. B. Glycerol monostearat oder Mischungen aus Mono-, Di- und Triglyceriden, Partialfettsäureester des Sorbitans und/oder bevorzugt Fett säureester des Polyglycerols wie beispielsweise Polyglycerol Polyricinoleat, die in einer Konzentration von 10 bis 1000 Gew.-%, vorzugsweise 100 bis 900 Gew.-%, besonders bevorzugt 400 bis 800 Gew.-%, bezogen auf das/die Carotinoid(e), verwendet werden.Here, a water-in-oil is used using an emulsifier. Emulsion formed in which the water phase protective colloid stabili contains carotenoid nanoparticles. Arrive as emulsifiers known W / O emulsifiers with an HLB value less than 10, ins particular from 2 to 6 into consideration (see H.P. Fiedler, Lexikon der Auxiliaries for pharmacy, cosmetics and related areas, 1996, pages 753 ff). Typical representatives of this emulsifier class are partial fatty acid esters of polyhydric alcohols such. B. Glycerol monostearate or mixtures of mono-, di- and triglycerides, Partial fatty acid esters of sorbitan and / or preferably fat acid esters of polyglycerol such as polyglycerol Polyricinoleate, which is in a concentration of 10 to 1000 wt .-%, preferably 100 to 900% by weight, particularly preferably 400 to 800% by weight, based on the carotenoid (s), can be used.
Das Dispersionsmittel kann sowohl mineralischen, pflanzlichen als auch tierischen Ursprungs sein. Typische Vertreter sind eßbare Öle, insbesondere Sesamöl, Maiskeimöl, Baumwollsaatöl, Sojabohne nöl oder Erdnußöl, Ester mittelkettiger pflanzlicher Fettsäuren sowie unterschiedliche Fischöle wie beispielsweise Makrelen-, Sprotten- oder Lachsöl. Die Menge des Dispersionsmittels beträgt im allgemeinen 30 bis 95, vorzugsweise 50 bis 80 Gew.-%, bezogen auf die Gesamtmasse der fertigen Emulsion.The dispersant can be mineral, vegetable or also be of animal origin. Typical representatives are edible Oils, in particular sesame oil, corn oil, cottonseed oil, soybean oil or peanut oil, esters of medium-chain vegetable fatty acids as well as different fish oils such as mackerel, Sprat or salmon oil. The amount of the dispersant is generally 30 to 95, preferably 50 to 80 wt .-%, based on the total mass of the finished emulsion.
Man kann das Emulgieren kontinuierlich oder diskontinuierlich durchführen.The emulsification can be carried out continuously or batchwise carry out.
Die physikalische Stabilität des doppelten Dispersionssystems, wie etwa die Sedimentationsstabilität, wird erreicht durch eine sehr gute Feinverteilung der Wasserphase in der Ölphase, z. B. durch intensive Behandlung mit einem Rotor/Stator-Dispergator bei Temperaturen von 20 bis 80, bevorzugt 40 bis 70°C oder mit einem Hochdruckhomogenisator wie einem APV Gaul in bzw. mit einem Höchstdruckhomogenisator wie dem Microfluidizer im Druckbereich von 700 bis 1000 bar. Die damit erreichbaren mittleren Durch messer der wäßrig-dispersen Phase sind kleiner 100 µm, bevorzugt kleiner 10 µm, insbesondere kleiner 1 µm.The physical stability of the double dispersion system, such as sedimentation stability is achieved through a very good fine distribution of the water phase in the oil phase, e.g. B. through intensive treatment with a rotor / stator disperser Temperatures of 20 to 80, preferably 40 to 70 ° C or with one High pressure homogenizer like an APV Gaul in or with a Ultra-high pressure homogenizer such as the microfluidizer in the pressure range from 700 to 1000 bar. The average throughput that can be achieved with it Knife of the aqueous disperse phase are smaller than 100 microns, preferred less than 10 µm, especially less than 1 µm.
Die nanopartikulären, schutzkolloidstabilisierten Carotinoide in der dispersen Phase gewährleisten außerdem, daß diese flüssige Formulierung die gleiche Bioverfügbarkeit und chemische Stabili tät aufweist wie die Trockenpulver gemäß EP-B-0 065 193.The nanoparticulate, protective colloid stabilized carotenoids in the disperse phase also ensure that it is liquid Formulating the same bioavailability and chemical stabili act as the dry powder according to EP-B-0 065 193.
Die so hergestellten, erfindungsgemäßen Flüssigformulierungen carotinoidhaltiger Wirkstoffe können zu Färbezwecken in der Aqua kultur direkt oder in der Regel nach Verdünnen mit Ölen auf das bereits fertig extrudierte Fischfutter aufgesprüht werden.The liquid formulations according to the invention thus produced Active substances containing carotenoids can be used for coloring purposes in the Aqua culture directly or usually after dilution with oils on the already extruded fish food can be sprayed on.
Im Lebensmittelbereich lassen sich die flüssigen Carotinoid-For mulierungen zum Färben von u. a. Margarine, Backwaren, Nudeln, Desertprodukte etc. einsetzen, wobei die erfindungsgemäßen W/O- Emulsionen besonders gut geeignet sind, wenn für das Färbever fahren eine Öllöslichkeit der Formulierung erforderlich ist. Aus anwendungstechnischer Sicht haben diese Flüssigformulierungen außerdem den Vorteil, daß sie einfacher dosierbar sind als ver gleichbare Carotinoid-Trockenpulver.In the food sector, the liquid carotenoid form formulations for dyeing u. a. Margarine, baked goods, pasta, Use desert products etc., the W / O- Emulsions are particularly suitable when used for dyeing drive an oil solubility of the formulation is required. Out In terms of application technology, these have liquid formulations also the advantage that they are easier to dose than ver comparable carotenoid dry powder.
Entsprechendes gilt für die Anwendung der erfindungsgemäßen Caro tinoid-Flüssigformulierungen zu Färbezwecken im Kosmetik- und Pharmabereich.The same applies to the application of the Caro according to the invention tinoid liquid formulations for coloring purposes in cosmetics and Pharmaceutical sector.
In den nachfolgenden Beispielen wird die Durchführung des erfin dungsgemäßen Verfahrens näher erläutert.In the following examples, the implementation of the inventions inventive method explained in more detail.
85 g einer Astaxanthin-Dispersion mit einem mittleren Teilchen durchmesser der Astaxanthin-Partikel von ungefähr 100 nm, die neben 6 Gew.-% Astaxanthin, 55 Gew.-% Wasser, 20 Gew.-% Saccha rose, 15 Gew.-% Gelatine, 2 Gew.-% Ethoxyquin, 1 Gew.-% Konser vierungsstoffe sowie 1 Gew.-% Ascorbylpalmitat enthält, wurden nach dem Mischkammermikronisierverfahren gemäß EP-B-0 065 193 hergestellt und anschließend bei 50°C 5 Minuten lang in ein Gemisch aus 300 g Sojaöl und 30 g Polyglycerol Polyricinoleat emulgiert. Die resultierende stabile Emulsion hatte einen Wirk stoffgehalt von ca. 1,2 Gew.-%.85 g of an astaxanthin dispersion with a medium particle diameter of the astaxanthin particles of approximately 100 nm, the in addition to 6% by weight of astaxanthin, 55% by weight of water, 20% by weight of saccha rose, 15% by weight gelatin, 2% by weight ethoxyquin, 1% by weight preserver Vation substances and 1 wt .-% contains ascorbyl palmitate according to the mixing chamber micronization process according to EP-B-0 065 193 prepared and then in at 50 ° C for 5 minutes Mixture of 300 g soybean oil and 30 g polyglycerol polyricinoleate emulsified. The resulting stable emulsion had an effect 1.2% by weight.
Bei Verwendung einer Zahnkranzdispergiermaschine (Ultraturax®) als Homogenisator wurden mittlere Tropfendurchmesser der disper sen Phase von ca. 2 µm erreicht. Bei zusätzlicher Anwendung eines Hochdruckhomogenisators (Mikrofluidizer) bei 1000 bar konnten mittlere Tropfendurchmesser von ca. 1 µm erzielt werden.When using a gear rim dispersion machine (Ultraturax®) As a homogenizer, the mean droplet diameters of the disper phase of approx. 2 µm. With additional application of a High pressure homogenizers (microfluidizers) at 1000 bar could average drop diameters of approx. 1 µm can be achieved.
193 g einer Canthaxanthin-Dispersion mit einem mittleren Teil chendurchmesser der Canthaxanthin-Partikel von ungefähr 150 nm, die neben 4 Gew.-% Canthaxanthin, 70 Gew.-% Wasser, 14 Gew.-% Saccharose, 9 Gew.-% Gelatine, 1 Gew.-% Ethoxyauin, 1 Gew.-% Kon servierungsstoffe sowie 1 Gew.-% Ascorbylpalmitat enthält, wurden nach dem Mischkammermikronisierverfahren gemäß EP-B-0 065 193 hergestellt und anschließend bei 60°C 2 Minuten lang in ein Ge misch aus 400 g Sojaöl und 40 g Polyglycerol Polyricinoleat mit Hilfe eines Ultraturax® bei 11000 U/min emulgiert. Zur Verbesse rung der Feinverteilung wurde die Emulsion zusätzlich bei ca. 26°C in zwei Passagen in einem Höchstdruckhomogenisator (Mikrofluidi zer) bei 900 bar homogenisiert. Die resultierende stabile Emul sion hatte einen Wirkstoffgehalt von ca. 1,2 Gew.-%. Die mittlere Tröpfengröße betrug 0,85 µm.193 g of a canthaxanthin dispersion with a central part diameter of the canthaxanthin particles of approximately 150 nm, which in addition to 4% by weight canthaxanthin, 70% by weight water, 14% by weight Sucrose, 9% by weight gelatin, 1% by weight ethoxyauin, 1% by weight con contains preservatives and 1% by weight of ascorbyl palmitate according to the mixing chamber micronization process according to EP-B-0 065 193 prepared and then in a Ge at 60 ° C for 2 minutes mix with 400 g soybean oil and 40 g polyglycerol polyricinoleate Emulsified using an Ultraturax® at 11000 rpm. For improvement The emulsion was also finely divided at approx. 26 ° C in two passages in a high-pressure homogenizer (microfluidic zer) homogenized at 900 bar. The resulting stable emul sion had an active ingredient content of approximately 1.2% by weight. The middle Droplet size was 0.85 µm.
Claims (8)
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19649062A DE19649062A1 (en) | 1996-11-27 | 1996-11-27 | Liquid, oil-miscible carotenoid preparations |
| DK97119150T DK0845503T3 (en) | 1996-11-27 | 1997-11-03 | Liquid, oil-miscible carotenoid compositions |
| AT97119150T ATE201893T1 (en) | 1996-11-27 | 1997-11-03 | LIQUID CAROTINOID PREPARATIONS MIXABLE WITH OIL |
| DE59703725T DE59703725D1 (en) | 1996-11-27 | 1997-11-03 | Liquid carotenoid preparations that are miscible with oil |
| EP97119150A EP0845503B1 (en) | 1996-11-27 | 1997-11-03 | Liquid carotenoid compound preparations miscible with oil |
| ES97119150T ES2158426T3 (en) | 1996-11-27 | 1997-11-03 | PREPARED OF LIQUID CAROTINOIDS, MISCIBLE WITH OIL. |
| PT97119150T PT845503E (en) | 1996-11-27 | 1997-11-03 | LIQUID COMPOSITIONS OF CAROTENOIDS MISCIBLE WITH OIL |
| TW086116717A TW529915B (en) | 1996-11-27 | 1997-11-10 | Liquid, oil-miscible carotenoid preparations |
| US08/972,392 US5863953A (en) | 1996-11-27 | 1997-11-18 | Liquid, oil-miscible carotenoid preparations |
| JP32293897A JP4608034B2 (en) | 1996-11-27 | 1997-11-25 | Liquid carotenoid preparations mixable with oil |
| CN97122957A CN1104234C (en) | 1996-11-27 | 1997-11-26 | Carotenoid preparation capable of mixing with liquid and oil |
| NO975441A NO308173B1 (en) | 1996-11-27 | 1997-11-26 | Liquid, oil-miscible carotenoid preparation |
| GR20010400801T GR3035945T3 (en) | 1996-11-27 | 2001-05-28 | Liquid carotenoid compound preparations miscible with oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19649062A DE19649062A1 (en) | 1996-11-27 | 1996-11-27 | Liquid, oil-miscible carotenoid preparations |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19649062A1 true DE19649062A1 (en) | 1998-05-28 |
Family
ID=7812881
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19649062A Withdrawn DE19649062A1 (en) | 1996-11-27 | 1996-11-27 | Liquid, oil-miscible carotenoid preparations |
| DE59703725T Expired - Lifetime DE59703725D1 (en) | 1996-11-27 | 1997-11-03 | Liquid carotenoid preparations that are miscible with oil |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE59703725T Expired - Lifetime DE59703725D1 (en) | 1996-11-27 | 1997-11-03 | Liquid carotenoid preparations that are miscible with oil |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5863953A (en) |
| EP (1) | EP0845503B1 (en) |
| JP (1) | JP4608034B2 (en) |
| CN (1) | CN1104234C (en) |
| AT (1) | ATE201893T1 (en) |
| DE (2) | DE19649062A1 (en) |
| DK (1) | DK0845503T3 (en) |
| ES (1) | ES2158426T3 (en) |
| GR (1) | GR3035945T3 (en) |
| NO (1) | NO308173B1 (en) |
| PT (1) | PT845503E (en) |
| TW (1) | TW529915B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10105305A1 (en) * | 2001-02-02 | 2002-08-14 | Nutrinova Gmbh | Sorbic acid preparation as a feed additive in livestock rearing |
| DE20109224U1 (en) * | 2001-06-01 | 2002-10-17 | Dr. Marcus GmbH & Co. KG, 21502 Geesthacht | Dye mixture for food, pharmaceuticals and cosmetics |
Families Citing this family (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2216079T3 (en) * | 1996-05-14 | 2004-10-16 | Dsm Ip Assets B.V. | PROCEDURE FOR THE ELABORATION OF CAROTENOID COMPOSITIONS. |
| JP2002513411A (en) | 1997-04-04 | 2002-05-08 | ヘンケル コーポレーション | Lutein ester with high bioavailability |
| DE19841930A1 (en) * | 1998-09-14 | 2000-03-16 | Basf Ag | Stable, powdery lycopene formulations containing lycopene with a degree of crystallinity greater than 20% |
| US6270782B1 (en) | 1999-10-22 | 2001-08-07 | Bath & Body Works, Inc. | Body spray composition with pearl-like oil phase droplets in container |
| US20030104090A1 (en) * | 2000-05-05 | 2003-06-05 | Levy Pedro E. | Supplements containing annatto extracts and carotenoids and methods for using the same |
| JP2002161031A (en) * | 2000-11-27 | 2002-06-04 | Noevir Co Ltd | Skin care preparation |
| US7105176B2 (en) * | 2000-11-29 | 2006-09-12 | Basf Aktiengesellschaft | Production of solid preparations of water-soluble, sparingly water-soluble or water-insoluble active compounds |
| DK1213013T3 (en) * | 2000-11-29 | 2007-07-02 | Basf Ag | Process for the preparation of solid compositions of water-soluble, heavily water-soluble or water-insoluble active substances |
| DE60317770T3 (en) | 2002-02-06 | 2013-07-25 | Dsm Ip Assets B.V. | astaxanthin |
| US6844020B2 (en) * | 2002-07-26 | 2005-01-18 | Kemin Foods, L.C. | Solutions of carotenoids for use in foods and personal care products |
| US7375133B2 (en) * | 2002-07-29 | 2008-05-20 | Cardax Pharmaceuticals, Inc. | Pharmaceutical compositions including carotenoid ether analogs or derivatives for the inhibition and amelioration of disease |
| US20050059659A1 (en) * | 2002-07-29 | 2005-03-17 | Lockwood Samuel Fournier | Carotenoid analogs or derivatives for controlling C-reactive protein levels |
| US7345091B2 (en) * | 2002-07-29 | 2008-03-18 | Cardax Pharmaceuticals, Inc. | Carotenoid ether analogs or derivatives for the inhibition and amelioration of disease |
| CN101845009B (en) * | 2002-07-29 | 2012-10-03 | 卡达克斯药物公司 | Structural carotenoid analogs for the inhibition and amelioration of disease |
| US7763649B2 (en) * | 2002-07-29 | 2010-07-27 | Cardax Pharmaceuticals, Inc. | Carotenoid analogs or derivatives for controlling connexin 43 expression |
| US20050143475A1 (en) * | 2002-07-29 | 2005-06-30 | Lockwood Samuel F. | Carotenoid analogs or derivatives for the inhibition and amelioration of ischemic reperfusion injury |
| US7521584B2 (en) * | 2002-07-29 | 2009-04-21 | Cardax Pharmaceuticals, Inc. | Carotenoid analogs or derivatives for the inhibition and amelioration of disease |
| US20050009788A1 (en) * | 2002-07-29 | 2005-01-13 | Lockwood Samuel Fournier | Carotenoid ester analogs or derivatives for controlling connexin 43 expression |
| US20050148517A1 (en) * | 2002-07-29 | 2005-07-07 | Lockwood Samuel F. | Carotenoid ether analogs or derivatives for controlling connexin 43 expression |
| US20050004235A1 (en) * | 2002-07-29 | 2005-01-06 | Lockwood Samuel Fournier | Carotenoid analogs or derivatives for the inhibition and amelioration of liver disease |
| US20050026874A1 (en) * | 2002-07-29 | 2005-02-03 | Lockwood Samuel Fournier | Carotenoid ether analogs or derivatives for the inhibition and amelioration of liver disease |
| US20050059635A1 (en) * | 2002-07-29 | 2005-03-17 | Lockwood Samuel Fournier | Carotenoid ester analogs or derivatives for controlling C-reactive protein levels |
| US7723327B2 (en) * | 2002-07-29 | 2010-05-25 | Cardax Pharmaceuticals, Inc. | Carotenoid ester analogs or derivatives for the inhibition and amelioration of liver disease |
| US20050049248A1 (en) * | 2002-07-29 | 2005-03-03 | Lockwood Samuel Fournier | Carotenoid ether analogs or derivatives for controlling C-reactive protein levels |
| US7320997B2 (en) * | 2002-07-29 | 2008-01-22 | Cardax Pharmaceuticals, Inc. | Pharmaceutical compositions including carotenoid ester analogs or derivatives for the inhibition and amelioration of disease |
| GB0218932D0 (en) * | 2002-08-14 | 2002-09-25 | Zoolife Internat Ltd | Composition for dietary enrichment |
| US20060058269A1 (en) * | 2004-04-14 | 2006-03-16 | Lockwood Samuel F | Carotenoid analogs or derivatives for the inhibition and amelioration of inflammation |
| WO2005102356A1 (en) * | 2004-04-14 | 2005-11-03 | Hawaii Biotech, Inc. | Carotenoid analogs or derivatives for the inhibition and amelioration of inflammation |
| US7351424B2 (en) * | 2004-07-22 | 2008-04-01 | Bio Lut S.A. De C.V. | Enhanced purity trans-lutein-ester compositions and methods of making same |
| MX2007002374A (en) * | 2004-08-31 | 2007-04-23 | Akzo Nobel Nv | Method for pigment solubilisation, a pigment composition and its use. |
| AU2005289383B2 (en) * | 2004-09-29 | 2011-10-06 | Michael Ary Bos | Caratenoid composition and method for preparation thereof |
| US8197851B2 (en) * | 2004-09-29 | 2012-06-12 | Michael Ary Bos | Carotenoid composition and method for preparation thereof |
| US7758884B2 (en) * | 2005-01-28 | 2010-07-20 | Kemin Industries, Inc. | Formulation for increasing the deposition of dietary carotenoids in eggs |
| JP5142988B2 (en) | 2005-05-23 | 2013-02-13 | ファレス ファーマシューティカル リサーチ エヌ．ブイ． | Direct dissolution |
| US20070065487A1 (en) * | 2005-09-21 | 2007-03-22 | Bio Lut S.A. De C.V. | Trans-lutein xantophyll ester of high purity and high bioavailability in micellar solution and a process for the preparation thereof |
| JP2007112744A (en) * | 2005-10-20 | 2007-05-10 | Toyo Seikan Kaisha Ltd | EXTRACT LIQUID CONTAINING beta-CRYPTOXANTHIN COMPONENT, AND FOOD AND DRINK AND SOAP OR COSMETIC OBTAINED BY INCORPORATING EXTRACT LIQUID |
| JP2007326829A (en) * | 2006-06-09 | 2007-12-20 | Fujifilm Corp | Emulsion composition |
| US7435846B2 (en) * | 2006-08-18 | 2008-10-14 | Industrial Organica, S.A. De C.V. | Absorption and bioavailability of carotenoids, formulations and applications |
| WO2008080037A2 (en) * | 2006-12-21 | 2008-07-03 | Isp Investments Inc. | Carotenoids of enhanced bioavailability |
| EP2111125B2 (en) * | 2007-01-16 | 2016-11-16 | Basf Se | Liquid formulations comprising carotenoids |
| US20100028444A1 (en) * | 2007-02-23 | 2010-02-04 | Basf Se | Use of water-dispersible carotenoid nanoparticles as taste modulators, taste modulators containing water-dispersible carotenoid nanoparticles, and, method for taste modulation |
| WO2008102018A2 (en) * | 2007-02-23 | 2008-08-28 | Basf Se | Method for modulating the taste of material compisitions containing at least one high intensity sweetener (his) |
| CN101396068B (en) * | 2007-09-27 | 2013-05-01 | 浙江医药股份有限公司新昌制药厂 | Carotenoid preparation and use thereof and feedstuff containing the preparation and preparation method thereof |
| EP2224823B2 (en) * | 2007-11-29 | 2021-11-17 | Basf Se | Pulverulent carotenoid preparation for colouring drinks |
| US20090162306A1 (en) * | 2007-12-21 | 2009-06-25 | Conopco, Inc., D/B/A Unilever | Topical composition comprising coloring antioxidants |
| US8877819B2 (en) * | 2008-10-02 | 2014-11-04 | Georgetown University | Methods for treating heat stress and related compositions |
| DK2343986T4 (en) * | 2008-10-07 | 2021-07-26 | Basf Se | READY TO USE, STABLE EMULSION |
| ES2400146T3 (en) | 2009-03-05 | 2013-04-05 | Basf Se | Powdery composition of astaxanthin derivatives l |
| ES2398724T3 (en) * | 2009-03-05 | 2013-03-21 | Basf Se | Formulation of astaxanthin derivatives and their application |
| EP2403362B1 (en) | 2009-03-05 | 2013-01-23 | Basf Se | Powdered compositions of astaxanthin derivatives ii |
| WO2010100232A2 (en) | 2009-03-05 | 2010-09-10 | Basf Se | Formulation of astaxanthin derivatives and use thereof iii |
| JP2012025712A (en) * | 2010-07-27 | 2012-02-09 | Jx Nippon Oil & Energy Corp | Anti-anxiety composition |
| US20120157547A1 (en) | 2010-12-21 | 2012-06-21 | Ricardo Montoya-Olvera | Compositions and applications of carotenoids of improved absorption and bioavailability |
| CN103391725B (en) * | 2011-02-18 | 2015-09-30 | 富士胶片株式会社 | Containing the composition of carotenoid |
| CN105188408B (en) | 2012-12-19 | 2019-03-01 | 诺华丝国际股份有限公司 | Lutein class composition and application method |
| CN104274428B (en) | 2013-07-09 | 2016-04-13 | 浙江新维普添加剂有限公司 | The preparation method of oil-dispersing property carotenoid formulation |
| JP6400956B2 (en) * | 2014-06-30 | 2018-10-03 | ユニ・チャーム株式会社 | Granular pet food manufacturing method |
| CN107156545B (en) * | 2017-05-23 | 2021-05-07 | 集美大学 | Bee bread containing astaxanthin and hydrophilic colloid and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1211911B (en) * | 1959-09-08 | 1966-03-03 | Hoffmann La Roche | Process for the production of a carotenoid preparation particularly suitable for coloring food and feed |
| GB993138A (en) * | 1961-11-22 | 1965-05-26 | Pfizer & Co C | Improvements in the preparation of vitamin-containing beadlets |
| US3998753A (en) * | 1974-08-13 | 1976-12-21 | Hoffmann-La Roche Inc. | Water dispersible carotenoid preparations and processes thereof |
| US3998759A (en) * | 1975-01-29 | 1976-12-21 | Universal Oil Products Company | Method of catalyst manufacture |
| DE3119383A1 (en) * | 1981-05-15 | 1982-12-02 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING FINE DISTRIBUTED, POWDERED CAROTINO PREPARATIONS |
| DE3702030A1 (en) * | 1987-01-24 | 1988-08-04 | Basf Ag | POWDERED, WATER-DISPERSIBLE CAROTINOID PREPARATIONS AND METHOD FOR THE PRODUCTION THEREOF |
| US5158798A (en) * | 1990-02-05 | 1992-10-27 | Pfizer Inc. | Low-calorie fat substitute |
| US5139800A (en) * | 1990-11-02 | 1992-08-18 | Pfizer Inc | Browning composition and process for browning foods |
| DE4141351A1 (en) * | 1991-12-14 | 1993-06-17 | Basf Ag | STABLE POWDERFUL VITAMIN AND / OR CAROTINOIDE PREPARATES AND PROCESS FOR THEIR PREPARATION |
| DK19393D0 (en) * | 1993-02-19 | 1993-02-19 | Danochemo As | PROCEDURE FOR PREPARING A WATER DISPERSIBLE POWDER-CAROTENOID PREPARATION |
| WO1996023420A1 (en) * | 1995-01-31 | 1996-08-08 | Neurosearch A/S | Astaxanthin suspension |
-
1996
- 1996-11-27 DE DE19649062A patent/DE19649062A1/en not_active Withdrawn
-
1997
- 1997-11-03 EP EP97119150A patent/EP0845503B1/en not_active Expired - Lifetime
- 1997-11-03 DK DK97119150T patent/DK0845503T3/en active
- 1997-11-03 ES ES97119150T patent/ES2158426T3/en not_active Expired - Lifetime
- 1997-11-03 AT AT97119150T patent/ATE201893T1/en not_active IP Right Cessation
- 1997-11-03 DE DE59703725T patent/DE59703725D1/en not_active Expired - Lifetime
- 1997-11-03 PT PT97119150T patent/PT845503E/en unknown
- 1997-11-10 TW TW086116717A patent/TW529915B/en not_active IP Right Cessation
- 1997-11-18 US US08/972,392 patent/US5863953A/en not_active Expired - Lifetime
- 1997-11-25 JP JP32293897A patent/JP4608034B2/en not_active Expired - Lifetime
- 1997-11-26 NO NO975441A patent/NO308173B1/en not_active IP Right Cessation
- 1997-11-26 CN CN97122957A patent/CN1104234C/en not_active Expired - Lifetime
-
2001
- 2001-05-28 GR GR20010400801T patent/GR3035945T3/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10105305A1 (en) * | 2001-02-02 | 2002-08-14 | Nutrinova Gmbh | Sorbic acid preparation as a feed additive in livestock rearing |
| DE20109224U1 (en) * | 2001-06-01 | 2002-10-17 | Dr. Marcus GmbH & Co. KG, 21502 Geesthacht | Dye mixture for food, pharmaceuticals and cosmetics |
Also Published As
| Publication number | Publication date |
|---|---|
| NO308173B1 (en) | 2000-08-07 |
| ATE201893T1 (en) | 2001-06-15 |
| NO975441L (en) | 1998-05-28 |
| PT845503E (en) | 2001-10-31 |
| EP0845503A3 (en) | 1999-05-19 |
| ES2158426T3 (en) | 2001-09-01 |
| EP0845503B1 (en) | 2001-06-06 |
| DK0845503T3 (en) | 2001-09-03 |
| GR3035945T3 (en) | 2001-08-31 |
| CN1104234C (en) | 2003-04-02 |
| US5863953A (en) | 1999-01-26 |
| JP4608034B2 (en) | 2011-01-05 |
| NO975441D0 (en) | 1997-11-26 |
| DE59703725D1 (en) | 2001-07-12 |
| CN1185433A (en) | 1998-06-24 |
| TW529915B (en) | 2003-05-01 |
| JPH10168333A (en) | 1998-06-23 |
| EP0845503A2 (en) | 1998-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0845503B1 (en) | Liquid carotenoid compound preparations miscible with oil | |
| EP1173521B1 (en) | Stable, aqueous dispersions and stable, water-dispersible dry powders of xanthophylls, and production and use of the same | |
| EP0278284B1 (en) | Pulverulent water-dispersible carotenoid compounds and process to prepare them | |
| EP0944675B1 (en) | Stable, aqueous dispersions and stable, water-dispersible dry xanthophyll powder, their production and use | |
| EP1228705B1 (en) | Process to produce dry powder of a carotenoid or several carotenoids | |
| EP0065193B1 (en) | Process for the manufacture of powdery, finely divided preparations of carotenoids or retinoids | |
| EP1794238B1 (en) | Method for producing dry powders of at least one carotenoid | |
| EP0832569B1 (en) | Preparing powdery carotenoide compounds dispersible in cold water and their use | |
| DE19841930A1 (en) | Stable, powdery lycopene formulations containing lycopene with a degree of crystallinity greater than 20% | |
| EP0795585A1 (en) | Finely divided suspensions of carotenoids or retinoids and process to manufacture them | |
| EP2111125B2 (en) | Liquid formulations comprising carotenoids | |
| EP1219292B1 (en) | Procedure or manufacturing dry powdered compositions comprising one or several oxygen-containing carotenoids | |
| WO2007003598A1 (en) | Aqueous suspensions of poorly water-soluble and water-insoluble active ingredients and drying powder produced therefrom | |
| WO2008087139A1 (en) | Unctuous compositions | |
| WO2010100232A2 (en) | Formulation of astaxanthin derivatives and use thereof iii | |
| WO2010100233A1 (en) | Method for producing solutions of astaxanthin derivatives | |
| WO2005075385A2 (en) | Method for producing dry powders of one or several carotenoids | |
| DE102005031467A1 (en) | Emulsifier system, emulsion and their use | |
| EP1761246A1 (en) | Aqueous dispersions of low-water-solubility or water-insoluble active substances and dry powders produced therefrom | |
| DE102004057587A1 (en) | Aqueous dispersions of a mixture of poorly water-soluble or water-insoluble active ingredients and a single-celled protein material and dry powder prepared therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8130 | Withdrawal |